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Derivation of Plank Einstain Constant
Derivation of Plank Einstain Constant
1 Planck-Einstein Relation E = hν
This is the equation relating energy to frequency. It was the earliest equation of quantum mechanics, imply-
ing that energy comes in multiples (“quanta”) of a fundamental constant h. It is written as either
E = hν
or
E = h̄ω
where h̄ = h/2π. ν is linear frequency and ω is angular frequency. The fundamental constant h is called
Planck’s constant and is equal to 6.62608 ×10−34 Js (h̄ = 1.05457 × 10−34 Js, or 1.05457 × 10−27 erg s).
This relation was first proposed by Planck in 1900 to explain the properties of black body radiation. The
interpretation was that matter energy levels are quantized. At the time this appeared compatible with the
notion that matter is composed of particles that oscillate. The discovery that the energy of electrons in
atoms is given by discrete levels also fitted well with the Planck relation. In 1905 Einstein proposed that the
same equation should hold also for photons, in his explanation of the photoelectric effect. The light incident
on a metal plate gives rise to a current of electrons only when the frequency of the light is greater than a
certain value. This value is associated with the energy required to remove an electron from the metal (the
“work function”). The electron is ejected only when the light energy matches the discrete electron binding
energy. Einstein’s proposal that the light energy is quantized just like the electron energy was more radical
at the time: light quantization was harder for people to accept than quantization of energy levels of matter
particles. (The word “photon” for these quantized packets of light energy came later, given by G. N. Lewis,
of Lewis Hall!)
Ψ;t = Lt Ψ; 0
Ψ;t Ψ;t = Ψ; 0 Ψ; 0
Hence we conclude that Lt† Lt = 1, i.e., Lt is unitary, so write as U(t). More precisely then,
Then we obtain
U(t) = [U(t/N)]N .
Now consider what happens as we make the time interval infinitesimal. As δt = t/N → 0, U(δt) → 1. We
can write an expression for this that is unitary to first order as
U(δt) = 1 − i∆(δt),
where the operator ∆ is Hermitian. What physical operator might ∆ correspond to? Here comes the physical
leap of analogy. First look at what the units of ∆ are; they are time−1 , i.e., the units of frequency. What
physical observable has units of frequency? The Planck-Einstein relation says that E = h̄ω where ω is fre-
quency and h̄ = h/2π, with h the fundamental Planck constant. So lets choose our operator ∆ to correspond
to energy divided by h̄. Now we know that in classical mechanics that the energy is given by the Hamiltonian
operator H = KE + PE and that this operator generates the time evolution. So in a simple leap of analogy,
lets take h̄∆ to be equal to the quantum mechanical Hamiltonian operator that corresponds to the total energy
of the quantum system, i.e., a sum of kinetic and potential energy operators. Then we have
i
U(δt) = 1 − Hδt.
h̄
The rest is plain sailing. We can either take the limit as N → ∞ to derive the exponential form exp[−iHt/h̄]
or, more simply, we use the composition law to write
∂U
ih̄ = HU(t).
∂t
This is the Schrodinger equation for the time evolution operator U(t). Rewriting the evolution operator in
its full form as U(t,t0 ) and multiplying on the right by Ψ;t0 , we find
∂U(t,t0 )
ih̄ Ψ;t0 = HU(t,t0 ) Ψ;t0 ,
∂t
which is equivalent to
∂ Ψ;t
ih̄ = H Ψ;t .
∂t
So we have arrived at the time dependent Schrodinger equation for the time evolution of the wave function
of a quantum system.
MH = H H , MV = V V .
A single measurement on an arbitrary state ψ will collapse ψ onto one of the two orthonormal basis
vectors. For example, if the H measurement is made, the state after measurement will be
H ψ
H q .
ψ H H ψ
If the measurement is repeated many times, this state will be obtained with probability
PH = | H ψ |2 .
Now consider a particle in a quantum state, e.g., the energy level of a hydrogen atom. The hydrogen atom
consists of 1 positively charged proton in the nucleus and 1 negatively charged electron. The electron is
∼ 1800 times lighter than the proton, so to a first approximation the electron can be regarded as moving
around a stationnary proton. The possible energy levels for this electronic motion form a discrete, infinite
set of levels of negative total energy (indicating overall binding to the proton), and are given by the relation
En ∼ −1/n2 , n = 1, 2, 3, ...... The energy eigenvectors n formed by these energy levels form an infinite
dimensional Hilbert space. Now what if we want to observe the electron? It is moving in configuration
space, so lets consider the effect of the measurement operator corresponding to a location r in configuration
space. The measurement operator is
Pr = r r
and a measurement on the ket ψ collapses this onto the state r r ψ , with probability
| r ψ |2 = |ψ(r)|2 .
So |ψ(r)| is the probability amplitude of finding an electron at r, i.e., “the wave function in the position
representation”. Note that the state after measurement is the position ket r .
We can understand this in a pictorial manner by imagining a basis consisting of a very densely spread set of
delta functions: the wave function is the amplitude of the the expansion of the quantum state in this basis.
ψ = ∑ αi ri
i
r ψ = ∑ αi r ri
i
= αi δ (r − ri )
= ψ(r).
where δ (r − r0 ) is the Dirac delta function. This is defined by the relation (shown here for 1D)
Z +∞
f (x0 )δ (x − x0 )dx0 = f (x).
−∞
Setting f (x) = 1 shows that the integral under the delta function is equal to unity. The three dimensional
delta function is given by
δ (r − r0 ) = δ (x − x0 )δ (y − y0 )δ (z − z0 ).
We can regard the Dirac delta function as the limit of a sequence of functions possessing unit norm, e.g., a
sequence of Gausssians with variable width λ :
1 0 2 2
fλ = √ exp−(x−x ) /2λ .
λ 2π
Note that the norm of the basis states r is ill-defined, unless one agrees to implicitly integrate over the
position coordinate and make use of the delta function property.
To summarize, the ket ψ can be expanded in the position representation as
Z
ψ = dr0 r0 r0 ψ
The inner product between two state ψ and φ can be expressed in terms of the corresponding wave
functions in the position representation:
Z
φ ψ = dr φ r r ψ
Z
= drφ ∗ (r)ψ(r).
which is just the orthonormality condition between φn and φm . We can make this set of functions a
basis for the Hilbert space spanned by the energy eigenstates n . This basis of wave functions in position
representation has a well behaved norm
Z
2
||φn || = |φn (r)|2 dr = 1.
where p0 ψ = ψ(p0 ) is the probability amplitude to find the particle with momentum p0 . It is the wave
function in the momentum representation. Note that equivalently, it can be understood as the expansion
coefficient in the expansion in momentum eigenstates p0 .
Projecting this expansion into the position representation yields the basic equation relating position and
momentum representations of a quantum state ψ :
Z
ψ(r) = r ψ = dp0 r p0 ψ(p0 ).
Note that using the Dirac notation we are correct in writing ψ on both right and left hand sides of this
equation. However, the two functions may have very different dependence on their respective variables r
and p. To avoid confusion, one usually gives these different names, e.g., ψ(r) and ψ̃(p).
Transformation between position and momentum representations
What is the transformation element r p0 in the above equation? If we set this equal to eip·r then the
equation looks like a Fourier transform of the wave function in momentum space, ψ̃(p), i.e.,
Z
ψ(r) = dpeip·r ψ̃(p).
This is not quite a Fourier transform, since we have momentum p rather than wave vector k in the integral.
However, p and k satisfy the de Broglie relation,
p = h̄k
4 The Hamiltonian
p 2
What is the Hamiltonian operator? Classically, the Hamiltonian is the energy operator, H = 2m + V (x).
Quantum mechanically, we would like to use either the position or momentum basis to represent the oper-
ator since then either x or p will be diagonal, and consequently also any corresponding functions of these
operators that occur in the Hamiltonian. Thus in a position representation V (x) is diagonal, while in a
p2
momentum representation 2m is diagonal. E.g.,
Z
V̂ = dxdx0 x x V x0 x0
Z
= dxdx0 x V (x)δ (x − x0 ) x
Z
= dx x V (x) x
h̄
p̂ = ∇.
i
For the derivation see ”Quantum Mechanics”, vol. 1, page 149, by Cohen-Tannoudji; ”Modern Quantum
Mechanics”, page 54, by Sakurai; ”Quantum mechanics”, chapter 4, by Dirac.
Hence the kinetic energy operator in the position representation is h̄2 /2m∇2 .
So, what if we had used the momentum representation? Then the kinetic energy would be simple, merely
the diagonal form p2 /2m and we would need to evaluate x in the momentum representation. This is given by
x = ih̄d/d p. Now suppose we had some non-trivial potential energy, e.g., V (x) = 1/cosh2 (x). This happens.
Then the potential energy would be given by V (p) = 1/cosh2 (ih̄d/d p) which is really not something that
you want to deal with in your partial differential equation for the wave function!
∂ h̄2 ∂ 2 ψ
ih̄ ψ(x,t) = − ψ(x,t) (1)
∂t 2m ∂ x2
h
with m the particle’s mass and h̄ = 2π . Recall that Planck’s constant has a value of h = 6.6 × 10−34 J · s. This
is a very small quantity with respect to ordinary macroscopic levels, and is the main reason why quantum
effects are not usually noticeable.
If we take this Schrodinger equation and plug in our trial solution ψ(x,t) = ei(kx−ω(k)t) , we find that this trial
2
solution works provided that ω(k) = h̄k2m . This is known as the dispersion relation for a free particle. Now,
notice that the most general solution is a linear superposition of such functions for many different k values:
Z
ψ(x,t) = dkAk ei(kx−ω(k)t) (2)
h̄k2
This superposition solution is known as a wave packet. The velocity of a wave packet is v = ∂∂ωk = ∂∂k 2m =
h̄k
m. This is the ”group velocity”. We can also quickly rearrange this to note that mv = h̄k. But what is ”mv”?
It’s the momentum, p! Therefore we conclude that p = h̄k. This is a relationship between the physical
momentum of a particle and the wave-vector of a wavefunction. We can illuminate this further as follows:
h 2π h
p = h̄k = = (3)
2π λ λ
This is known as the DeBroglie relation, and it actually predates the Schrodinger equation.
h̄2 ∂ 2
Ĥ = KE + PE = − +V (x) (4)
2m ∂ x2
To be clear about the distinction between operators and functions, we’ll denote quantum mechanical opera-
tors with ”hats”, e.g. Ĥ or p̂.
The Schrodinger Equation
∂
ih̄ ψ(x,t) = Ĥψ(x,t) (5)
∂t
defines the relationship between the energy of a system ( through Ĥ) and its time development. Can we
understand this relationship better?
First, we note that this is a partial differential equation, which means that it is a differential equation with
more than one variable (x and t in this case). We now employ a handy math trick for partial differential
equations, and assume that the solution to the Schrodinger Equation can be written as the product ψ(x,t) =
ψ(x)φ (t). This is called separation of variables. If we plug this into the Schr. Eqn. and divide both sides
by ψ(x)φ (t) :
∂φ
∂ Ĥψ(x)
ih̄ψ(x) φ (t) = φ (t)Ĥψ(x) → ih̄ ∂t = (6)
∂t φ (t) ψ(x)
The left hand side (LHS) is a function of t, and the right hand side (RHS) is a function of x. Therefore, for
this solution to make sense for all possible x and t, both sides must equal a constant. What is that constant?
Why, energy, of course!
So, the Schr. eqn. breaks into two equations, one in time (t) and one in space (x):
∂ φ (t)
time : ih̄ = Eφ (t) (8)
∂t